Silicone-modified comb polymers based on acryloydimethy taurine acid (2-acrylamido-2-methyl-1-propanesulfonic acid)

ABSTRACT

The invention provides water-soluble or water-swellable copolymers obtained by free-radical copolymerization of A) acryloyldimethyltaurine and/or acryloyldimethyltaurates, B) optionally, one or more olefinically unsaturated, optionally crosslinking comonomers containing at least one oxygen, nitrogen, sulfur or phosphorus atom and possessing a molecular weight of less than 500 g/mol, C) one or more at least monofunctional, silicon-containing components capable of free-radical polymerization, the copolymerization 
     D) taking place in the presence of at least one polymeric additive having number-average molecular weights of from 200 g/mol to 10 9  g/mol. The water-soluble or water-swellable copolymers of the present invention are useful in paper processing, laundry detergents, textile processing, petroleum extraction and formulating cosmetics.

Silicon-modified comb polymers based on acryloyldimethyltaurine acid.

The present invention relates to silicon-modified comb polymers based onacryloyldimethyltaurine and/or acryloyldimethyltaurates.

In recent years water-soluble polymers have acquired a continuallyincreasing importance in industry and science. In volume terms,polyelectrolytes are occupying a very large proportion of the overallannual production. They find application, for example, in paperprocessing, in the laundry detergents industry, in textile processing,in petroleum extraction or as important base materials for cosmetics.

In the cosmetics sector a key role is accorded to polyelectrolytes.Besides water-soluble surface-active substances there is a high demandin this sector for systems which thicken oil and water. Thickeners ofthis kind, particularly the “super-absorbents” prepared on the basis ofpolyacrylic acid, have progressed since their development in the 1970sto become a pillar of the hygiene sector. In their crosslinked versions,partly or fully neutralized polyacrylic acids and their water-solublecopolymers are employed in numerous cosmetic formulations as bodyingagents. The diversity of possible structures and the diverse possibleapplications associated therewith are manifested not least in a host ofpatents filed worldwide since the mid-1970s.

In the 1990s, innovative thickeners based on2-acrylamido-2-methyl-1-propane-sulfonic acid (AMPS) and their saltswere introduced into the market (EP 816 403 and WO 98/00094). In bothhomopolymer and copolymer form (®Aristoflex AVC, Clariant GmbH) suchthickeners are superior in many respects to the correspondingpolycarboxylates (Carbopols). For example, thickener systems based onAMPS display outstanding properties in pH ranges below pH 6, i.e., in apH range in which it is no longer possible to operate with conventionalpolycarboxylate thickeners. Moreover, the microgel structure of suchthickeners leads to a particularly pleasant skin sensation. The ease ofprocessing and the favorable toxicological profile of the principalmonomer imbue these thickeners with a high application potential.

Over recent years representatives of a new thickener design have enteredthe market. In these thickeners, two different properties have beencombined in one polymer, thereby opening up new fields of application.Thickening emulsifiers or dispersants are but two examples of this newclass of substance. Brand names that may be mentioned include thePemulens® TR-1 and TR-2 from BF Goodrich or the Aculyn® products fromRohm & Haas. All existing versions are based on hydrophobically modifiedversions of the conventional polyacrylates.

The aim of this invention was to synthesize a new class of polymer basedon the concept of the molecular combination of properties, intended toallow the formulator to stabilize and/or to thicken aqueous systemscontaining silicone oil. Through free-radical copolymerization ofacryloyldimethyltaurine (AMPS) and/or acryloyldimethyltaurates, in thepresence where appropriate of further comonomers or polymeric additives,and suitable vinylic mono- or polyfunctional silicone derivatives, itproved possible to synthesize both crosslinked and noncrosslinkedstructures having advantageous performance properties. A particularpossibility with the newly developed structures is the stabilization ofsilicone-containing emulsions with very high fractions of silicone oil(>30%). Advantageously, emulsions of this kind display a very pleasantskin sensation.

The invention provides water-soluble or water-swellable copolymersobtainable by free-radical copolymerization of

-   -   A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,    -   B) if desired, one or more olefinically unsaturated, optionally        crosslinking comonomers containing at least one oxygen,        nitrogen, sulfur or phosphorus atom and possessing a molecular        weight of less than 500 g/mol,    -   C) one or more at least monofunctional, silicon-containing        components capable of free-radical polymerization, the        copolymerization    -   D) taking place in the presence of at least one polymeric        additive having number-average molecular weights of from 200        g/mol to 10⁹ g/mol.

The copolymers of the invention preferably possess a molecular weight offrom 10³ g/mol to 10⁹ g/mol, more preferably from 10⁴ to 10⁷ g/mol, verypreferably from 5*10⁴ to 5*10⁶ g/mol.

The acryloyldimethyltaurates can be the organic or inorganic salts ofacryloyl-dimethyltaurine. Preference is given to the Li⁺, Na⁺, K⁺, Mg⁺⁺,Ca⁺⁺, Al⁺⁺⁺ and/or NH₄ ⁺ salts. Likewise preferred are themonoalkylammonium, dialkylammonium, trialkylammonium and/ortetraalkylammonium salts, in which the alkyl substituents of the aminesmay independently of one another be (C₁-C₂₂)-alkyl radicals which ifdesired may be occupied by up to 3 (C₂-C₁₀)-hydroxyalkyl groups.Preference is also given to mono- to triethoxylated ammonium compoundswith a different degree of ethoxylation. It should be noted that theinvention also embraces mixtures of two or more of the abovementionedrepresentatives.

The degree of neutralization of the acryloyldimethyltaurine can bebetween 0 and 100%, particular preference being given to a degree ofneutralization of more than 80%.

Based on the total mass of the copolymers, the amount ofacryloyldimethyltaurine and/or acryloyidimethyltaurates is at least 0.1%by weight, preferably from 20 to 99.5% by weight, more preferably from50 to 98% by weight.

As comonomers B) it is possible to use all olefinically unsaturatedmonomers whose reaction parameters allow copolymerization withacryloyidimethyltaurine and/or acryloyidimethyltaurates in therespective reaction media. Preferred comonomers B) are unsaturatedcarboxylic acids and their anhydrides and salts, and also their esterswith aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromaticalcohols having a carbon number of from 1 to 22. Particularly preferredunsaturated carboxylic acids are acrylic acid, methacrylic acid,styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconicacid, and senecic acid. Preferred counterions are Li⁺, Na⁺, K⁺, Mg⁺⁺,Ca⁺⁺, Al⁺⁺⁺, NH₄ ⁺, monoalkylammonium, dialkylammonium, trialkylammoniumand/or tetraalkylammonium radicals, in which the alkyl substituents ofthe amines independently of one another are (C₁-C₂₂)-alkyl radicals or(C₂-C₁₀)-hydroxyalkyl radicals. It is additionally possible to employmono- to triethoxylated ammonium compounds with a different degree ofethoxylation.

The degree of neutralization of the carboxylic acids can be between 0and 100%, and more preferably is above 80%.

Further preferred comonomers are open-chain N-vinyl amides, preferablyN-vinyl-formamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide(VIMA) and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams)with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) andN-vinylcaprolactam; amides of acrylic and methacrylic acid, preferablyacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylatedacrylamides and methacrylamides, preferably hydroxyethyl methacrylate,hydroxymethylmethacrylamide, hydroxyethylmethacrylamide,hydroxypropylmethacrylamide, andmono[2-(methacryloyloxy)ethyl]succinate; N,N-dimethylamino methacrylate;diethylaminomethyl methacrylate; acrylamido- and methacrylamidoglycolicacid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate;styrene; acrylonitrile; vinyl chloride; stearyl acrylate; laurylmethacrylate; vinylidene chloride; and/or tetrafluoroethylene.

Likewise suitable comonomers B) are inorganic acids and their salts andesters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid,allylphosphonic acid, and methallylsulfonic acid.

The weight fraction of the comonomers B), based on the total mass of thecopolymers, can be from 0 to 99.8% by weight and is preferably from 0.5to 80% by weight, more preferably from 2 to 50% by weight.

Suitable polymerizable silicone-containing components C) are allcompounds which are olefinically at least monounsaturated and capable offree-radical copolymerization under the reaction conditions chosen ineach case with acryloyl-dimethyltaurine and/or acryloyldimethyltaurateand, if desired, further comonomers. The distribution of the individualsilicone-containing monomers across the polymer chains which form neednot necessarily be random. The invention also embraces the formation,for example, of blocklike (including multiblock) or gradientlikestructures. Combinations of two or more different silicone-containingrepresentatives are also possible. The use of silicone-containingcomponents having two or more polymerization-active groups leads to theconstruction of branched or crosslinked structures.

Preferred silicon-containing components are those of formula (I)R′-Z-[(Si(R³R⁴)—O—)_(w)—(Si(R⁵R⁶)—O)_(x)—]—R²  (I)

In this formula R¹ represents a polymerizable function from the group ofthe vinylically unsaturated compounds which is suitable for thesynthesis of polymeric structures by a free-radical route. R¹ representspreferably a vinyl, allyl, methallyl, methylvinyl, acryloyl(CH₂═CH—CO—), methacryloyl (CH₂═C[CH₃]—CO—), crotonyl, senecionyl,itaconyl, maleyl, fumaryl or styryl radical.

The attachment of the silicone-containing polymer chain to the reactiveend group R¹ sometimes requires a suitable chemical bridge Z. Preferredbridges Z are —O—, —((C₁-C₅₀)alkylene)-, —((C₆-C₃₀)arylene)-,—((C₅-C₈)cycloalkylene)-, —((C₁-C₅₀)— alkenylene)-, -(polypropyleneoxide)_(n)-, -(polyethylene oxide)_(o)-, -(polypropyleneoxide)_(n)(polyethylene oxide)_(o)-, where n and o independently of oneanother denote numbers from 0 to 200 and the distribution of the EO/POunits can be random or in the form of blocks. Further suitable bridgegroups Z are —((C₁-C₁₀)alkyl)-(Si(OCH₃)₂)— and —(Si(OCH₃)₂)—.

The polymeric central moiety is represented by silicone-containingrepeating units. The radicals R³, R⁴, R⁵, and R⁶ denote independently ofone another —CH₃, —O—CH₃, —C₆H₅ or —O—C₆H₅.

The indices w and x represent stoichiometric coefficients which amountindependently of one another to from 0 to 500, preferably 10 to 250.

The distribution of the repeating units across the chain can be not onlypurely random but also blocklike, alternating or gradientlike.

R² can first symbolize an aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁-C₅₀) hydrocarbon radical (linear orbranched) or —OH, —NH₂, —N(CH₃)₂, —R⁷ or stand for the structural unit[-Z-R¹]. The definition of the two variables Z and R¹ has already beenexplained. R⁷ stands for further Si-containing groups. Preferred R⁷radicals are —O—Si(CH₃)₃, —O—Si(Ph)₃, —O—Si(O—Si(CH₃)₃)₂CH₃), and—O—Si(O—Si(Ph)₃)₂Ph).

If R² is an element of the group [-Z-R¹] the monomers in question aredifunctional monomers which can be used to crosslink the polymerstructures which form. Formula (I) describes not onlysilicone-containing polymer species with vinylic functionalization and apolymer-typical distribution, but also defined compounds having discretemolecular weights.

Particularly preferred silicone-containing components are the followingsuch components with acrylic or methacrylic modification:

methacryloyloxypropyldimethylsilyl-endblocked polydimethylsiloxanes (f=2to 500)

methacryloyloxypropyl-endblocked polydimethylsiloxanes (f=2 to 500)

vinyldimethoxysilyl-endblocked polydimethylsiloxanes (f=2-500).

The weight fraction of the comonomers D), based on the total mass of thecopolymers, is from 0.1 to 99.9% by weight, preferably from 0.1 to 50%by weight, more preferably from 0.2 to 40% by weight, and verypreferably from 0.5 to 30% by weight.

In one preferred embodiment the copolymerization is conducted in thepresence of at least one polymeric additive D), the additive D) beingadded wholly or partly in solution to the polymerization medium beforethe actual copolymerization. The use of two or more additives D) islikewise in accordance with the invention. Crosslinked additives D) maylikewise be used.

The additives D) or mixtures thereof must only be wholly or partlysoluble in the chosen polymerization medium.

During the actual polymerization step the additive D) has a number offunctions. On the one hand it prevents the formation of overcrosslinkedpolymer fractions in the copolymer which forms in the actualpolymerization step, and on the other hand the additive D) isstatistically attacked by active free radicals in accordance with thevery well-known mechanism of graft copolymerization. Depending on theparticular additive D), this results in greater or lesser fractions ofthe additive being incorporated into the copolymers. Moreover, suitableadditives D) possess the property of altering the solution parameters ofthe copolymers which form during the free-radical polymerizationreaction in such a way that the average molecular weights are shifted tohigher values. As compared with analogous copolymers prepared withoutthe addition of the additives D), those prepared with the addition ofadditives D) advantageously exhibit a significantly higher viscosity inaqueous solution.

Preferred additives D) are homopolymers and copolymers which are solublein water and/or alcohols. The term “copolymers” also comprehends thosehaving more than two different monomer types.

Particularly preferred additives D) are homopolymers and copolymers ofN-vinyl-formamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide,propylene oxide, acryloyldimethyltaurine, N-vinylcaprolactam,N-vinylmethylacetamide, acrylamide, acrylic acid, methacrylic acid,N-vinylmorpholide, hydroxyethyl methacrylate, diallyldimethylammoniumchloride (DADMAC) and/or [2-(methacryloyloxy)ethyl]tri-methylammoniumchloride (MAPTAC); polyalkylene glycols and/or alkylpolyglycols.Particularly preferred additives D) are polyvinylpyrrolidones (e.g.,K15®, K20® and K30® from BASF), poly(N-vinylformamides),poly(N-vinylcaprolactams), and copolymers of N-vinylpyrrolidone,N-vinylformamide and/or acrylic acid, which may also have been partly orfully hydrolyzed.

The molecular weight of the additives D) is preferably from 10³ to 10⁷g/mol, more preferably from 0.5*10⁴ to 10⁶ g/mol.

The amount in which the polymeric additive D) is used, based on thetotal mass of the monomers to be polymerized during thecopolymerization, is preferably from 0.1 to 90% by weight, morepreferably from 1 to 20% by weight, and with particular preference from1.5 to 10% by weight.

In another preferred embodiment the copolymers of the invention arecrosslinked, i.e., they contain comonomers having at least twopolymerizable vinyl groups. Preferred crosslinkers aremethylenebisacrylamide; methylenebismethacrylamide; esters ofunsaturated monocarboxylic and polycarboxylic acids with polyols,preferably di-acrylates and tri-acrylates and/or -methacrylates, morepreferably butanediol and ethylene glycol diacrylate and/ormethacrylate, trimethylolpropane triacrylate (TMPTA) andtrimethylolpropane trimethacrylate (TMPTMA); allyl compounds, preferablyallyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polyallylesters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine;allyl esters of phosphoric acid; and/or vinylphosphonic acidderivatives.

A particularly preferred crosslinker is trimethylolpropanetrimethacrylate (TMPTMA).

The weight fraction of crosslinking comonomers, based on the total massof the copolymers, is preferably up to 20% by weight, more preferablyfrom 0.05 to 10% by weight, and very preferably from 0.1 to 7% byweight.

The polymerization medium used may comprise all organic or inorganicsolvents which have a very substantially inert behavior with respect tofree-radical polymerization reactions and which advantageously allow theformation of medium or high molecular weights. Those used preferablyinclude water; lower alcohols; preferably methanol, ethanol, propanols,iso-, sec- and t-butanol, very preferably t-butanol; hydrocarbons having1 to 30 carbon atoms, and mixtures of the aforementioned compounds.

The polymerization reaction takes place preferably in the temperaturerange between 0 and 150° C., more preferably between 10 and 100° C.,either at atmospheric pressure or under elevated or reduced pressure. Ifdesired the polymerization may also be performed under an inert gasatmosphere, preferably under nitrogen.

In order to initiate the polymerization it is possible to usehigh-energy electro-magnetic rays, mechanical energy, or the customarychemical polymerization initiators, such as organic peroxides, e.g.,benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketoneperoxide, cumene hydroperoxide, dilauroyl peroxide (DLP) or azoinitiators, such as azodiisobutyronitrile (AIBN), for example. Likewisesuitable are inorganic peroxy compounds, such as (NH₄)₂S₂O₈, K₂S₂O₈ orH₂O₂, for example, where appropriate in combination with reducing agents(e.g., sodium hydrogensulfite, ascorbic acid, iron(II) sulfate, etc.) orredox systems comprising as reducing component an aliphatic or aromaticsulfonic acid (e.g., benzenesulfonic acid, toluenesulfonic acid, etc.).

The polymerization reaction can be conducted, for example, as aprecipitation polymerization, emulsion polymerization, solutionpolymerization, bulk polymerization or gel polymerization. Particularlyadvantageous for the profile of properties of the copolymers of theinvention is precipitation polymerization, preferably in tert-butanol.

The copolymers of the invention put the user in a position for the firsttime to thicken silicone oils, possibly in high concentration, in water,or else, in the case of highly modified versions, to thicken siliconeoils themselves. Accordingly, formulations with a strong silicone oilcharacter in stick form or gel form, for example, become possiblewithout the deleterious liquid consistency of oils.

It is additionally possible using the polymers of the invention toprepare emulsions with conventional oils which contain Si-containingemulsifiers (possibly also silicone oils), since this combines theproperties of silicone oils and conventional oils and also enables thestability of the emulsion by thickening the phases. All of theseemulsions exhibit an extremely good gloss, which is of greatsignificance for a cosmetic emulsion. A particular feature is theoutstanding skin sensation of these formulations as compared withconventional formulations. In the case of applications in the haircosmetology segment, the pleasant conditioning effect of the polymers isevident, as are the ease of combing and the shine.

The copolymers of the invention can be employed, inter alia, in W/Oemulsions, O/W emulsions, skin protection formulations, shampoos,rinses, treatments, decorative cosmetics such as lipsticks, lipcaresticks or lotions, etc., makeup such as liquid makeup, cover and resistmakeup, makeup powder, etc., stick deodorants, antiperspirants, bodywashes, liquid soap, bar soap, cleansing milk, sun protectionformulations, permanent waves, hair colorants, hair gels, and hairsprays, to name but a few. In the case of face makeup, for example, itshould be emphasized that by using the polymers of the invention it ispossible to absorb excess sebum.

The following examples serve to illustrate the invention without,however, restricting it thereto.

EXAMPLE 1

Reactants amount (g) NH₄ acryloyldimethyltaurate 80Vinyldimethoxyethyl-endblocked 20 dimethicone ( ® GP-501, Genesee Pol.Corp.) t-Butanol 400 Dilauroyl peroxide (initiator) 1Poly-N-vinylpyrrolidone ( ® K-15 BASF) 5

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of DLP. The polymer was isolatedby removal of the solvent under suction and by subsequent vacuum drying.In 1% strength aqueous solution the polymer exhibits a viscosity of 45000 mPas with a slightly opalescent appearance. The skin sensation ofthe gel is markedly superior to that of silicone-free versions.

EXAMPLE 2

Reactants amount (g) NH₄ acryloyldimethyltaurate 70 N-Vinylpyrrolidone 5Methacryloyloxypropyldimethicone 15 ( ® GP-446, Genesee Pol. Corp.)Isopropanol 500 Azobisisobutyronitrile (initiator) 1

The polymer was prepared by the solution polymerization method inisopropanol. The monomers were dissolved in the corresponding alcohol,the reaction mixture was rendered inert, and then, after initialheating, the reaction was initiated by addition ofdiazoisobutyronitrile. The polymer solution was subsequentlyconcentrated and the polymer was isolated by vacuum drying.

EXAMPLE 3

Reactants amount (g) Acryloyldimethyltaurine (AMPS) 80Methacryloyloxypropyldimethicone 20 ( ® GP-478, Genesee Pol. Corp.)Cyclohexane 200 Water 300 ® Span 80 (sorbitan ester) 1 Na₂S₂O₈(initiator) 1

The polymer was prepared by the emulsion method in water. The monomerswere emulsified in water/cyclohexane using Span® 80, the reactionmixture was rendered inert using N₂, and then, after initial heating,the reaction was initiated by addition of sodium peroxodisulfate. Thepolymer emulsion was subsequently evaporated down (with cyclohexaneacting as azeotrope former for water) and the polymer was therebyisolated.

EXAMPLE 4

Reactants amount (g) NH₄ acryloyldimethyltaurate 80 Monofunctionalizedethoxylated siloxane 15 (methacrylic, ® Silvet Y-12867, Witco) t-Butanol300 Dilauroyl peroxide 1

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of DLP. The polymer was isolatedby removal of the solvent under suction and by subsequent vacuum drying.

In 1% strength solution in distilled water the polymer exhibited a clearappearance with a viscosity of 35 000 mPas. In comparison thereto thesilicone-free version, with the same composition, exhibited a similarappearance and a viscosity of 12 000 mPas under identical measurementconditions. The skin sensation of the silicone-containing polymer ismarkedly improved over that of the comparison standards.

EXAMPLE 5

Reactants amount (g) Na acryloyldimethyltaurate 50 Monofunctionalized(methacrylically), 45 ethoxylated siloxane (® Silvet 7608 WITCO)t-Butanol 300 Trimethylolpropane triacrylate 1.8 Azabisamidopropylhydrochloride 1 Poly[N-vinylformamide] 8

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of ABAH. The polymer was isolatedby removal of the solvent under suction and by subsequent vacuum drying.

1. A water-soluble or water-swellable copolymer obtained by free-radicalcopolymerization of A) acryloyldimethyltaurine and/oracryloyldimethyltaurates, B) optionally, one or more olefinicallyunsaturated, comonomer containing at least one oxygen, nitrogen, sulfuror phosphorus atom and possessing a molecular weight of less than 500g/mol, C) one or more at least monofunctional, silicon-containingcomponent capable of free-radical polymerization, at least onesilicon-containing component being a compound selected from the groupconsisting of

where f=2 to 500

where f=2 to 500

where f=2 to 500, and mixtures thereof, the copolymerization D)optionally taking place in the presence of at least one polymericadditive having number-average molecular weights of from 200 g/mol to10⁹ g/mol.
 2. The water-soluble or water-swellable copolymer as claimedin claim 1, wherein component C) comprises further compounds of formula(I)R′-Z-[(Si(R³R⁴)—O—)_(w)—(Si(R⁵R⁶)—O)_(x)—]—R²  (I) where R₁ is a radicalselected from the group consisting of vinyl, allyl, methallyl,methylvinyl, acryloyl, methacryloyl, crotonyl, senecionyl, itaconyl,maleyl, fumaryl, styryl, and mixtures thereof; Z is a chemical bridge,R³, R⁴, R⁵, and R⁶ independently of one another denote —CH₃, —O—CH₃,—C₆H₅ or —O—C₆H₅; w, x denote numbers from 0 to 500, it being necessaryfor either w or x to be greater than zero, and R² is a saturated orunsaturated, aliphatic, cycloaliphatic, arylaliphatic or aromaticradical having in each case 1 to 50 carbon atoms or is a group of theformulae —OH, —NH₂, —N(CH₃)₂, —R⁷ or a group -Z-R¹, where Z and R¹ havethe definitions stated above and R⁷ is a group of the formula—O—Si(CH₃)₃, —O—Si(phenyl)₃, —O—Si(O—Si(CH₃)₃)₂CH₃) and—O—Si(O—Si(phenyl)₃)₂phenyl).
 3. The water-soluble or water-swellablecopolymer as claimed in claim 1, further containing one or morecomonomer B).
 4. The water-soluble or water-swellable copolymer asclaimed in claim 3, wherein the comonomer B is selected from the groupconsisting of unsaturated carboxylic acids, salts of unsaturatedcarboxylic acids, anhydrides of unsaturated carboxylic acids, esters ofunsaturated carboxylic acids with aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic alcohols having 1 to 22 carbon atoms,open-chain N-vinyl amides, cyclic N-vinyl amides having a ring size offrom 3 to 9, amides of acrylic acid, amides of methacrylic acid, amidesof substituted acrylic acids, amides of substituted methacrylic acids,2-vinylpyridine, 4-vinylpyridine, vinyl acetate; styrene, acrylonitrile,vinyl chloride, vinylidene chloride, tetrafluoroethylene,vinylphosphonic acid or the esters or salts thereof, vinylsulfonic acidor the esters or salts thereof, allylphosphonic acid or the esters orsalts thereof and/or methallylsulfonic acid or the esters or saltsthereof, and mixtures thereof.
 5. The water-soluble or water-swellablecopolymer of claim 1, wherein the copolymerization takes place in thepresence of at least one polymeric additive D).
 6. The water-soluble orwater-swellable copolymer as claimed in claim 5, wherein the polymericadditive D) is selected from the group consisting of polyalkyleneglycol, alkylpolyglycol, and mixtures thereof or a homopolymer orcopolymer of a compound selected from the group consisting ofN-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide,propylene oxide, acryloyl-dimethyltaurine, N-vinylcaprolactam,N-vinylmethylacetamide, acrylamide, acrylic acid, methacrylic acid,N-vinylmorpholide, hydroxymethyl methacrylate, DADMAC, MAPTAC, andmixtures thereof.
 7. The water-soluble or water-swellable copolymer asclaimed in claim 6, wherein the polymeric additive D) is selected fromthe group consisting of poly(N-vinylformamides),poly(N-vinylcaprolactams), and copolymers of a compound selected fromthe group consisting of N-vinyl-pyrrolidone, N-vinylformamide, acrylicacid, and mixtures thereof.
 8. The water-soluble or water-swellablecopolymer of claim 1, wherein the copolymer is crosslinked.
 9. Thewater-soluble or water-swellable copolymer of claim 1, wherein thecopolymer is copolymerized by precipitation polymerization intert-butanol.
 10. The water-soluble or water-swellable copolymer ofclaim 2, wherein the chemical bridge Z is selected from the groupconsisting of —O—, —((C₁-C₅₀)alkylene)-, —((C₆-C₃₀)arylene)-,—((C₅-C₈)cycloalkylene)-, —((C₁-C₅₀)alkenylene)-, -(polypropyleneoxide)_(n)-, -(polyethylene oxide)_(o)-, -(polypropyleneoxide)_(n)(polyethylene oxide)_(o)-, and mixtures thereof, where n and oindependently of one another denote numbers from 0 to 200 and having adistribution of EO/PO units being random or in block form.
 11. Thewater-soluble or water-swellable copolymer of claim 2, wherein thechemical bridge Z is —((C₁-C₁₀)alkyl)-(Si(OCH₃)₂)— and/or —(Si(OCH₃)₂)—.12. A water-soluble or water-swellable copolymer obtained byfree-radical copolymerization of acryloyldimethyltaurine and/oracryloyldimethyltaurates and one or more at least monofunctional,silicon-containing component capable of free-radical polymerization, atleast one silicon-containing component being a compound selected fromthe group consisting of

where f=2 to 500,

where f=2 to 500,

where f=2 to 500, and mixtures thereof.
 13. The water-soluble orwater-swellable copolymer of claim 12, further comprising one or moreolefinically unsaturated, comonomer containing at least one oxygen,nitrogen, sulfur or phosphorus atom and possessing a molecular weight ofless than 500 g/mol.
 14. The water-soluble or water-swellable copolymerof claim 12, wherein said copolymerization takes place in the presenceof at least one polymeric additive having number-average molecularweights of from 200 g/mol to 10⁹ g/mol.